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72 results on '"Rousse, A."'

1. Revealing the Elusive Structure and Reactivity of Iron Boride α-FeB

Author

Fernando Igoa Saldaña, Emile Defoy, Daniel Janisch, Gwenaëlle Rousse, Pierre-Olivier Autran, Anissa Ghoridi, Amandine Séné, Marzena Baron, Leopoldo Suescun, Yann Le Godec, David Portehault, Novel Advanced Nano-Objects (LCMCP-NANO), Matériaux Hybrides et Nanomatériaux (LCMCP-MHN), Laboratoire de Chimie de la Matière Condensée de Paris (LCMCP), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Laboratoire de Chimie de la Matière Condensée de Paris (LCMCP), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Design et étude de nouveaux matériaux à propriété remarquables [IMPMC] (IMPMC_DEMARE), Institut de minéralogie, de physique des matériaux et de cosmochimie (IMPMC), Muséum national d'Histoire naturelle (MNHN)-Institut de recherche pour le développement [IRD] : UR206-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Muséum national d'Histoire naturelle (MNHN)-Institut de recherche pour le développement [IRD] : UR206-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Collège de France - Chaire Chimie du solide et énergie, Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Réseau sur le stockage électrochimique de l'énergie (RS2E), Aix Marseille Université (AMU)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Nantes Université (Nantes Univ)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), European Synchroton Radiation Facility [Grenoble] (ESRF), Laboratorio de Cristalografıa, Estado Solido y Materiales [UCUR] (Cryssmat-Lab), Universidad de la República [Montevideo] (UDELAR), and Doctoral School ED397ESRF proposal MA-5188

Subjects
Inorganic Chemistry, crystal structure, borides, intergrowth, in situ XRD, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, Physical and Theoretical Chemistry, FAULTS
Abstract

International audience; Crystal structures can strongly deviate from bulk states when confined into nanodomains. These deviations may deeply affect properties and reactivity and then call for a close examination. In this work, we address the case where extended crystal defects spread through a whole solid and then yield an aperiodic structure and specific reactivity. We focus on iron boride, α-FeB, whose structure has not been elucidated yet, thus hindering the understanding of its properties. We synthesize the two known phases, α-FeB and β-FeB, in molten salts at 600 and 1100 °C, respectively. The experimental X-ray diffraction (XRD) data cannot be satisfactorily accounted for by a periodic crystal structure. We then model the compound as a stochastic assembly of layers of two structure types. Refinement of the powder XRD pattern by considering the explicit scattering interference of the different layers allows quantitative evaluation of the size of these domains and of the stacking faults between them. We, therefore, demonstrate that α-FeB is an intergrowth of nanometer-thick slabs of two structure types, β-FeB and CrB-type structures, in similar proportions. We finally discuss the implications of this novel structure on the reactivity of the material and its ability to perform insertion reactions by comparing the reactivities of α-FeB and β-FeB as reagents in the synthesis of a model layered material: Fe2AlB2. Using synchrotron-based in situ X-ray diffraction, we elucidate the mechanisms of the formation of Fe2AlB2. We highlight the higher reactivity of the intergrowth α-FeB in agreement with structural relationships.

Published
2023

2. Revealing the Elusive Structure and Reactivity of Iron Boride α-FeB

Author

Igoa Saldaña, Fernando, primary, Defoy, Emile, additional, Janisch, Daniel, additional, Rousse, Gwenaëlle, additional, Autran, Pierre-Olivier, additional, Ghoridi, Anissa, additional, Séné, Amandine, additional, Baron, Marzena, additional, Suescun, Leopoldo, additional, Le Godec, Yann, additional, and Portehault, David, additional

Published
2023
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3. Stacking Versatility in Alkali-Mixed Honeycomb Layered NaKNi2TeO6

Author

Gwenaëlle Rousse, François Weill, François Fauth, Montse Casas-Cabanas, Jon Serrano-Sevillano, Marie-Liesse Doublet, Romain Berthelot, Bernard Fraisse, Dany Carlier, Danielle Laurencin, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), CIC ENERGIGUNE - Parque Tecnol Alava, Institut de Chimie de la Matière Condensée de Bordeaux (ICMCB), Université de Bordeaux (UB)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), CELLS ALBA, Barcelona 08290, Spain, Advanced Lithium Energy Storage Systems - ALISTORE-ERI (ALISTORE-ERI), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Ikerbasque - Basque Foundation for Science, Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), The BL04-MSPD staff of CELLS-ALBA synchrotron is acknowledged for granting beamtime through InHouse quota (proposal 2020014011)., Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), and Basque Foundation for Science (Ikerbasque)

Subjects
Diffraction, Chemistry, Sodium, Stacking, Honeycomb (geometry), Oxides, Context (language use), [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, Nuclear magnetic resonance spectroscopy, 010402 general chemistry, 021001 nanoscience & nanotechnology, Alkali metal, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, Chemical physics, Cations, Potassium, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Density functional theory, Physical and Theoretical Chemistry, Layers, 0210 nano-technology, Stacking fault
Abstract

International audience; The reaction between P2-type honeycomb layered oxides Na2Ni2TeO6 and K2Ni2TeO6 enables the formation of NaKNi2TeO6. The compound is characterized by X-ray diffraction and 23Na solid-state nuclear magnetic resonance spectroscopy, and the structure is discussed through density functional theory calculations. In addition to the honeycomb Ni/Te cationic ordering, NaKNi2TeO6 exhibits a unique example of alternation of sodium and potassium layers instead of a random alkali-mixed occupancy. Stacking fault simulations underline the impact of the successive position of the Ni/Te honeycomb layers and validate the presence of multiple stacking sequences within the powder material, in proportions that evolve with the synthesis conditions. In a broader context, this work contributes to a better understanding of the alkali-mixed layered compounds.

Published
2021

4. Structural Polymorphism in Na4Zn(PO4)2 Driven by Rotational Order–Disorder Transitions and the Impact of Heterovalent Substitutions on Na-Ion Conductivity

Author

Vladimir Pomjakushin, François Fauth, Yaroslava Shakhova, Maria A. Kirsanova, Matthieu Courty, Artem M. Abakumov, Jean-Marie Tarascon, Sujoy Saha, Gwenaëlle Rousse, Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Sorbonne Université (SU), Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), European Synchrotron Radiation Facility (ESRF), Paul Scherrer Institute (PSI), Center for Electrochemical Energy Storage, Skolkovo Institute of Science and Technology, 3 Nobel Street, 143026 Moscow, Russia., Institut Universitaire de France (IUF), Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.), Advanced Lithium Energy Storage Systems - ALISTORE-ERI (ALISTORE-ERI), and Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Chemistry, Cationic polymerization, [CHIM.MATE]Chemical Sciences/Material chemistry, Electron, Conductivity, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, Crystallography, Polymorphism (materials science), Vacancy defect, Fast ion conductor, Ionic conductivity, Physical and Theoretical Chemistry, Powder diffraction
Abstract

International audience; Solid electrolytes have regained tremendous interest recently in light of the exposed vulnerability of current rechargeable battery technologies. While designing solid electrolytes, most efforts concentrated on creating structural disorder (vacancies, interstitials, etc.) in a cationic Li/Na sublattice to increase ionic conductivity. In phosphates, the ionic conductivity can also be increased by rotational disorder in the anionic sublattice, via a paddle-wheel mechanism. Herein, we report on Na4Zn(PO4)(2) which is designed from Na3PO4, replacing Na+ with Zn2+ and introducing a vacancy for charge balance. We show that Na4Zn(PO4)(2) undergoes a series of structural transitions under temperature, which are associated with an increase in ionic conductivity by several orders of magnitude. Our detailed crystallographic study, combining electron, neutron, and X-ray powder diffraction, reveals that the room-temperature form, alpha-Na4Zn(PO4)(2), contains orientationally ordered PO4 groups, which undergo partial and full rotational disorder in the high-temperature beta- and gamma-polymorphs, respectively. We furthermore showed that the highly conducting gamma-polymorph could be stabilized at room temperature by ball-milling, whereas the beta-polymorph can be stabilized by partial substitution of Zn2+ with Ga2+ and Al3+. These findings emphasize the role of rotational disorder as an extra parameter to design new solid electrolytes.

Published
2020

5. Stacking Versatility in Alkali-Mixed Honeycomb Layered NaKNi

Author

Romain, Berthelot, Jon, Serrano-Sevillano, Bernard, Fraisse, François, Fauth, François, Weill, Danielle, Laurencin, Montse, Casas-Cabanas, Dany, Carlier, Gwenaëlle, Rousse, and Marie-Liesse, Doublet

Abstract

The reaction between P2-type honeycomb layered oxides Na

Published
2021

6. Stacking Versatility in Alkali-Mixed Honeycomb Layered NaKNi2TeO6

Author

Berthelot, Romain, primary, Serrano-Sevillano, Jon, additional, Fraisse, Bernard, additional, Fauth, François, additional, Weill, François, additional, Laurencin, Danielle, additional, Casas-Cabanas, Montse, additional, Carlier, Dany, additional, Rousse, Gwenaëlle, additional, and Doublet, Marie-Liesse, additional

Published
2021
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7. Alkali-Glass Behavior in Honeycomb-Type Layered Li3–xNaxNi2SbO6 Solid Solution

Author

Emmanuelle Suard, Paula Sanz-Camacho, Yohan Biecher, Matthieu Saubanère, Coélio Vallée, Gwenaëlle Rousse, Bernard Fraisse, Dany Carlier, Romain Berthelot, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Institut de Chimie de la Matière Condensée de Bordeaux (ICMCB), Université de Bordeaux (UB)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Laue-Langevin (ILL), ILL, Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), ANR-10-LABX-0076,STORE-EX,Laboratory of excellency for electrochemical energy storage(2010), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), and Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)

Subjects
Diffraction, Layered oxides, solid-solution, 010405 organic chemistry, Neutron diffraction, Oxide, chemistry.chemical_element, honeycomb ordering, [CHIM.MATE]Chemical Sciences/Material chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, Alkali metal, 01 natural sciences, alkali mixed occupancy, 0104 chemical sciences, Inorganic Chemistry, Crystallography, chemistry.chemical_compound, chemistry, Honeycomb, Lithium, Density functional theory, Physical and Theoretical Chemistry, Solid solution
Abstract

International audience; Layered oxide compositions Li3–xNaxNi2SbO6 have been prepared by solid-state synthesis. A complete solid solution is evidenced and characterized by X-ray and neutron diffraction as well as 7Li and 23Na solid-state nuclear magnetic resonance spectroscopy. The transition-metal layer is characterized by the classic honeycomb Ni2+/Sb5+ ordering, whereas a more uncommon randomly mixed occupancy of lithium and sodium is evidenced within the alkali interslab space. In situ X-ray diffraction and density functional theory calculations show that this alkali disordered feature is entropically driven. Fast cooling then appears as a synthesis root to confine bidimensional alkali glass within crystalline layered oxides.

Published
2019

8. Electron Precise Sodium Carbaboride Nanocrystals from Molten Salts: Single Sources to Boron Carbides

Author

Gwenaëlle Rousse, Cristina Coelho-Diogo, Christel Gervais, Simon Delacroix, Fernando Igoa, Yann Le Godec, David Portehault, Yang Song, Novel Advanced Nano-Objects (LCMCP-NANO), Matériaux Hybrides et Nanomatériaux (LCMCP-MHN), Laboratoire de Chimie de la Matière Condensée de Paris (LCMCP), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Laboratoire de Chimie de la Matière Condensée de Paris (LCMCP), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut de minéralogie, de physique des matériaux et de cosmochimie (IMPMC), Muséum national d'Histoire naturelle (MNHN)-Institut de recherche pour le développement [IRD] : UR206-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut des matériaux de Paris-Centre (IMPC), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Spectroscopie, Modélisation, Interfaces pour L'Environnement et la Santé (LCMCP-SMiLES), Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), HPC resources from GENCI-IDRIS (Grant 097535), and Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)

Subjects
Octahedral cluster, 010405 organic chemistry, chemistry.chemical_element, Nanoparticle, Crystal structure, Boron carbide, [CHIM.MATE]Chemical Sciences/Material chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, chemistry, X-ray photoelectron spectroscopy, Chemical engineering, Physical and Theoretical Chemistry, Boron, Powder diffraction, Solid solution
Abstract

International audience; Boron-rich solids exhibit specific crystal structures and unique properties, which are only very scarcely addressed in nanoparticles. In this work, we address the original inorganic structural chemistry and reactivity of boron-rich nanoparticles, by reporting the first occurrence of sodium carbaboride nanocrystals based on the NaB 5 C crystal structure. To design these sub-10 nm nano-objects, we use liquid-phase synthesis in molten salts at 900°C. By combining a set of characterization tools including powder Xray powder diffraction, transmission electron microscopy, solid-state nuclear magnetic resonance coupled to DFT modeling, and X-ray photoelectron spectroscopy, we demonstrate that these nanocrystals deviate from the ideal stoichiometry reported for the bulk compound. We suggest that the carbon and sodium contents compensate each other to ensure that the octahedral cluster-based framework is stabilized by fulfilling an electron counting rule. These nanocrystals encompass substituted octahedral covalent structural building units not reported in the related bulk compound. They then shed new light on the ability of nanoparticles to host wide solid solution ranges in covalent solids and then to yield new solids. We finally show that these nanocrystals are efficient single sources of boron and carbon to form a nanostructured boron carbide, thus paving the way to new nanostructured materials.

Published
2021

10. Structural Polymorphism in Na

Author

Sujoy, Saha, Gwenaëlle, Rousse, Matthieu, Courty, Yaroslava, Shakhova, Maria, Kirsanova, François, Fauth, Vladimir, Pomjakushin, Artem M, Abakumov, and J M, Tarascon

Abstract

Solid electrolytes have regained tremendous interest recently in light of the exposed vulnerability of current rechargeable battery technologies. While designing solid electrolytes, most efforts concentrated on creating structural disorder (vacancies, interstitials, etc.) in a cationic Li/Na sublattice to increase ionic conductivity. In phosphates, the ionic conductivity can also be increased by rotational disorder in the anionic sublattice, via a paddle-wheel mechanism. Herein, we report on Na

Published
2020

11. Influence of Temperature-Driven Polymorphism and Disorder on Ionic Conductivity in Li6Zn(P2O7)2

Author

Gwenaëlle Rousse, Jean-Marie Tarascon, Vladimir Pomjakushin, Sujoy Saha, François Fauth, Collège de France - Chaire Chimie du solide et énergie, Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Université Pierre et Marie Curie - Paris 6 (UPMC), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), and Paul Scherrer Institute (PSI)

Subjects
010405 organic chemistry, Chemistry, Crystal chemistry, Cell volume, [CHIM.MATE]Chemical Sciences/Material chemistry, Activation energy, Crystal structure, Conductivity, Solid state electrolyte, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, Polymorphism (materials science), Chemical physics, Ionic conductivity, Physical and Theoretical Chemistry
Abstract

Ionic conductivity in a compound is rooted in a delicate interplay between its crystal structure and its structural defects (vacancies, interstitials, etc.). Hence, understanding this interplay is of utmost importance to design new solid state electrolytes. To shed some light on the above query, we investigated the rich crystal chemistry of Li6Zn(P2O7)2. This compound undergoes multiple structural transitions under the influence of temperature, which increases the conductivity by several orders and lowers the activation energy. We explained this jump in conductivity by the increased disorder associated with cation mixing. Our structural exploration indicates that both the room-temperature α-polymorph and the high-temperature ζ-polymorph crystallize in a C2/c space group but with a much smaller unit cell volume for the latter. While their structural framework based on P2O74– is similar, the ζ-polymorph presents a fully disordered Li/Zn sublattice, while it is fully ordered for the α-polymorph. Furthermore,...

Published
2018

12. Impact of Structural Polymorphism on Ionic Conductivity in Lithium Copper Pyroborate Li6CuB4O10

Author

Jean-Marie Tarascon, Daniel Alves Dalla Corte, Florian Strauss, Gwenaëlle Rousse, Carlotta Giacobbe, Robert Dominko, Collège de France - Chaire Chimie du solide et énergie, Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Advanced Lithium Energy Storage Systems - ALISTORE-ERI (ALISTORE-ERI), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), European Synchrotron Radiation Facility (ESRF), Laboratory for Materials Electrochemistry, and National Institute of Chemistry

Subjects
Chemistry, Analytical chemistry, chemistry.chemical_element, [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, Crystal structure, Conductivity, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Copper, 0104 chemical sciences, Dielectric spectroscopy, Inorganic Chemistry, Polymorphism (materials science), visual_art, visual_art.visual_art_medium, Ionic conductivity, Ceramic, Physical and Theoretical Chemistry, 0210 nano-technology, Boron
Abstract

The search for high Li-ion conducting ceramics has regained tremendous interest triggered by the renaissance of the all-solid-state battery. Within this context we herein reveal the impact of structural polymorphism of lithium copper pyroborate Li6CuB4O10 on its ionic conductivity. Using combined in situ synchrotron X-ray and neutron powder diffraction, a structural and synthetic relationship between α- and β-Li6CuB4O10 could be established and its impact on ionic conductivity evolution was followed using electrochemical impedance spectroscopy. We show that the high temperature form of Li6CuB4O10 exhibits a high Li-ion conductivity (2.7 mS cm–1 at 350 °C) and solve its crystal structure for the first time. Our results emphasize the significant impact of structural phase transitions on ionic conductivity and show possible high Li-ion mobility within borate based compounds.

Published
2018

13. Structural Instability Driven by Li/Na Competition in Na(Li

Author

Arnaud J, Perez, Gwenaëlle, Rousse, and Jean-Marie, Tarascon

Abstract

With increasing hopes placed on the Na-ion battery technology to complement the current Li-ion battery systems, it is important to improve the energy density of Na-based cathode materials. Na-rich rocksalt oxides, Na

Published
2019

14. Denticity and Mobility of the Carbonate Groups in AMCO3F Fluorocarbonates: A Study on KMnCO3F and High Temperature KCaCO3F Polymorph

Author

Hania Ahouari, Jean-Marie Tarascon, Artem M. Abakumov, Gwenaëlle Rousse, Vladimir Pomjakushin, Nadir Recham, Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Paul Scherrer Institute (PSI), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), Collège de France - Chaire Chimie du solide et énergie, Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), and Skolkovo Institute of Science and Technology [Moscow] (Skoltech)

Subjects
Phase transition, Denticity, [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, Crystal structure, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Synchrotron, 0104 chemical sciences, law.invention, Inorganic Chemistry, chemistry.chemical_compound, Crystallography, chemistry, Electron diffraction, law, Group (periodic table), Phase (matter), Carbonate, Physical and Theoretical Chemistry, 0210 nano-technology
Abstract

International audience; We report on a thorough structural study on two members of layered fluorocarbonates KMCO3F (M = Ca, Mn). The Ca-based member demonstrates a phase transition at similar to 320 degrees C, evidenced for the first time. The crystal structure of the high temperature phase (HT-KCaCO3F) was solved using neutron powder diffraction. A new Mn-based phase KMnCO3F was synthesized, and its crystal structure was solved from electron diffraction tomography data and refined from a combination of X-ray synchrotron and neutron powder diffraction. In contrast to other members of the fluorocarbonate family, the carbonate groups in the KMnCO3F and HT-KCaCO3F structures are not fixed to two distinct orientations corresponding to mono- and bidentate coordinations of the M cation. In KMnCO3F, the carbonate group can be considered as nearly "monodentate", forming one short (2.14 angstrom) and one long (3.01 angstrom) MnO contact. This topology provides more flexibility to the MCO3 layer and enables diminishing the mismatch between the MCO3 and KF layers. This conclusion is corroborated by the HT-KCaCO3F structure, in which the carbonate groups can additionally be tilted away from the layer plane thus relieving the strain arising from geometrical mismatch between the layers. The correlation between denticity of the carbonate groups, their mobility, and cation size variance is discussed. KMnCO3 orders antiferromagnetically below T-N = 40 K.

Published
2017

17. Magnetic Structures of Orthorhombic Li2M(SO4)2 (M = Co, Fe) and LixFe(SO4)2 (x = 1, 1.5) Phases

Author

Gwenaëlle Rousse, Jean-Marie Tarascon, Laura Lander, Marine Reynaud, Juan Rodríguez-Carvajal, Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université Pierre et Marie Curie - Paris 6 (UPMC), Chaire Chimie du solide et énergie, Chimie du solide et de l'énergie (CSE), Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU), CICEnergigune, Institut Laue-Langevin (ILL), ILL, Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), Collège de France - Chaire Chimie du solide et énergie, and Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Neutron powder diffraction, magnetic structure, Li-ion batteries, 02 engineering and technology, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, law.invention, Inorganic Chemistry, Condensed Matter::Materials Science, magneto-electric effect, Transition metal, law, Antiferromagnetism, Physical and Theoretical Chemistry, sulfates, neutron powder diffraction, Spins, Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, super- super-exchange interactions, Cathode, 0104 chemical sciences, Crystallography, Octahedron, magnetism, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Condensed Matter::Strongly Correlated Electrons, Orthorhombic crystal system, 0210 nano-technology, Néel temperature
Abstract

International audience; We report herein on the magnetic properties and structures of orthorhombic Li2M(SO4)2 (M = Co, Fe) and their oxidized phases LixFe(SO4)2 (x = 1, 1.5), which were previously studied as potential cathode materials for Li-ion batteries. The particular structure of these orthorhombic compounds (space group Pbca) consists of a three-dimensional network of isolated MO6 octahedra enabling solely super-super-exchange interactions between transition metals. We studied the magnetic properties of these phases via temperature-dependent susceptibility measurements and applied neutron powder diffraction experiments to solve their magnetic structures. All compounds present an antiferromagnetic long-range ordering of the magnetic spins below their Néel temperature. Their magnetic structures are collinear and follow a spin sequence (+ + – – – – + +), with the time reversal associated with the inversion center, a characteristic necessary for a linear magneto-electric effect. We found that the orientation of the magnetic moments varies with the nature of M. While Li2Co(SO4)2 and Li1Fe(SO4)2 adopt the magnetic space group Pb′c′a′, the magnetic space group for Li2Fe(SO4)2 and Li1.5Fe(SO4)2 is P1121′/a, which might hint for a possible monoclinic distortion of their nuclear structure. Moreover we compared the orthorhombic phases to their monoclinic counterparts as well as to the isostructural orthorhombic Li2Ni(SO4)2 compound. Finally, we show that this possible magneto-electric feature is driven by the topology of the magnetic interactions.

Published
2016

18. Alkali-Glass Behavior in Honeycomb-Type Layered Li

Author

Coélio, Vallée, Matthieu, Saubanère, Paula, Sanz-Camacho, Yohan, Biecher, Bernard, Fraisse, Emmanuelle, Suard, Gwenaëlle, Rousse, Dany, Carlier, and Romain, Berthelot

Abstract

Layered oxide compositions Li

Published
2019

19. Influence of Temperature-Driven Polymorphism and Disorder on Ionic Conductivity in Li

Author

Sujoy, Saha, Gwenaëlle, Rousse, François, Fauth, Vladimir, Pomjakushin, and Jean-Marie, Tarascon

Abstract

Ionic conductivity in a compound is rooted in a delicate interplay between its crystal structure and its structural defects (vacancies, interstitials, etc.). Hence, understanding this interplay is of utmost importance to design new solid state electrolytes. To shed some light on the above query, we investigated the rich crystal chemistry of Li

Published
2018

21. Denticity and Mobility of the Carbonate Groups in AMCO

Author

Gwenaelle, Rousse, Hania, Ahouari, Vladimir, Pomjakushin, Jean-Marie, Tarascon, Nadir, Recham, and Artem M, Abakumov

Abstract

We report on a thorough structural study on two members of layered fluorocarbonates KMCO

Published
2017

22. Synthesis, Structure, and Electrochemical Properties of K-Based Sulfates K

Author

Laura, Lander, Gwenaëlle, Rousse, Dmitry, Batuk, Claire V, Colin, Daniel Alves, Dalla Corte, and Jean-Marie, Tarascon

Abstract

Stabilizing new host structures through potassium extraction from K-based polyanionic materials has been proven to be an interesting approach to develop new Li

Published
2017

23. Synthesis, structure, and electrochemical properties of k-based sulfates <tex>K_{2}M_{2}(SO_{4})_{3}$</tex>) with M = Fe and Cu

Author

Gwenaëlle Rousse, Jean-Marie Tarascon, Laura Lander, Claire V. Colin, Dmitry Batuk, Daniel Alves Dalla Corte, Collège de France - Chaire Chimie du solide et énergie, Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), Université Pierre et Marie Curie - Paris 6 (UPMC), University of Antwerp (UA), Matériaux, Rayonnements, Structure (NEEL - MRS), Institut Néel (NEEL), Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Chaire Chimie du solide et énergie, Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), and Matériaux, Rayonnements, Structure (MRS)

Subjects
Diffraction, Langbeinite, Chemistry, Potassium, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrochemistry, 01 natural sciences, Synchrotron, 0104 chemical sciences, law.invention, Inorganic Chemistry, Crystallography, law, Phase (matter), [CHIM]Chemical Sciences, Neutron, Orthorhombic crystal system, Physical and Theoretical Chemistry, 0210 nano-technology
Abstract

International audience; Stabilizing new host structures through potassium extraction from K-based polyanionic materials has been proven to be an interesting approach to develop new Li+/Na+ insertion materials. Pursuing the same trend, we here report the feasibility of preparing langbeinite “Fe2(SO4)3” via electrochemical and chemical oxidation of K2Fe2(SO4)3. Additionally, we succeeded in stabilizing a new K2Cu2(SO4)3 phase via a solid-state synthesis approach. This novel compound crystallizes in a complex orthorhombic structure that differs from that of langbeinite as deduced from synchrotron X-ray and neutron powder diffraction. Electrochemically, the performance of this new phase is limited, which we explain in terms of sluggish diffusion kinetics. We further show that K2Cu2(SO4)3 decomposes into K2Cu3O(SO4)3 on heating, and we report for the first time the synthesis of fedotovite K2Cu3O(SO4)3. Finally, the fundamental attractiveness of these S = 1/2 systems for physicists is examined by neutron magnetic diffraction, which reveals the absence of a long-range ordering of Cu2+ magnetic moments down to 1.5 K.

Published
2017

24. Synthesis, Structure, and Electrochemical Properties of Na

Author

Florian, Strauss, Gwenaëlle, Rousse, Moulay Tahar, Sougrati, Daniel Alves, Dalla Corte, Matthieu, Courty, Robert, Dominko, and Jean-Marie, Tarascon

Abstract

In the search for new cathode materials for sodium ion batteries, the exploration of polyanionic compounds has led to attractive candidates in terms of high redox potential and cycling stability. Herein we report the synthesis of the two new sodium transition-metal pentaborates Na

Published
2016

25. Magnetic Structures of Orthorhombic Li

Author

Laura, Lander, Marine, Reynaud, Juan, Rodríguez-Carvajal, Jean-Marie, Tarascon, and Gwenaëlle, Rousse

Abstract

We report herein on the magnetic properties and structures of orthorhombic Li

Published
2016

26. Denticity and Mobility of the Carbonate Groups in AMCO3F Fluorocarbonates: A Study on KMnCO3F and High Temperature KCaCO3F Polymorph

Author

Rousse, Gwenaelle, Ahouari, Hania, Pomjakushin, Vladimir, Tarascon, Jean-Marie, Recham, Nadir, and Abakumov, Artem M.

Abstract

We report on a thorough structural study on two members of layered fluorocarbonates KMCO3F (M = Ca, Mn). The Ca-based member demonstrates a phase transition at ∼320 °C, evidenced for the first time. The crystal structure of the high temperature phase (HT-KCaCO3F) was solved using neutron powder diffraction. A new Mn-based phase KMnCO3F was synthesized, and its crystal structure was solved from electron diffraction tomography data and refined from a combination of X-ray synchrotron and neutron powder diffraction. In contrast to other members of the fluorocarbonate family, the carbonate groups in the KMnCO3F and HT-KCaCO3F structures are not fixed to two distinct orientations corresponding to mono- and bidentate coordinations of the M cation. In KMnCO3F, the carbonate group can be considered as nearly “monodentate”, forming one short (2.14 Å) and one long (3.01 Å) Mn–O contact. This topology provides more flexibility to the MCO3layer and enables diminishing the mismatch between the MCO3and KF layers. This conclusion is corroborated by the HT-KCaCO3F structure, in which the carbonate groups can additionally be tilted away from the layer plane thus relieving the strain arising from geometrical mismatch between the layers. The correlation between denticity of the carbonate groups, their mobility, and cation size variance is discussed. KMnCO3orders antiferromagnetically below TN= 40 K.

Published
2024
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27. Magnetic Structures of Orthorhombic Li2M(SO4)2(M = Co, Fe) and LixFe(SO4)2(x= 1, 1.5) Phases

Author

Lander, Laura, Reynaud, Marine, Rodríguez-Carvajal, Juan, Tarascon, Jean-Marie, and Rousse, Gwenaëlle

Abstract

We report herein on the magnetic properties and structures of orthorhombic Li2M(SO4)2(M = Co, Fe) and their oxidized phases LixFe(SO4)2(x= 1, 1.5), which were previously studied as potential cathode materials for Li-ion batteries. The particular structure of these orthorhombic compounds (space group Pbca) consists of a three-dimensional network of isolated MO6octahedra enabling solely super-super-exchange interactions between transition metals. We studied the magnetic properties of these phases via temperature-dependent susceptibility measurements and applied neutron powder diffraction experiments to solve their magnetic structures. All compounds present an antiferromagnetic long-range ordering of the magnetic spins below their Néel temperature. Their magnetic structures are collinear and follow a spin sequence (+ + – – – – + +), with the time reversal associated with the inversion center, a characteristic necessary for a linear magneto-electric effect. We found that the orientation of the magnetic moments varies with the nature of M. While Li2Co(SO4)2and Li1Fe(SO4)2adopt the magnetic space group Pb′c′a′, the magnetic space group for Li2Fe(SO4)2and Li1.5Fe(SO4)2is P1121′/a, which might hint for a possible monoclinic distortion of their nuclear structure. Moreover we compared the orthorhombic phases to their monoclinic counterparts as well as to the isostructural orthorhombic Li2Ni(SO4)2compound. Finally, we show that this possible magneto-electric feature is driven by the topology of the magnetic interactions.

Published
2024
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32. Synthesis, Structure, and Magnetic Properties of the NaCoXO4F·2H2O Phases Where X = S and Se

Author

Gwenaëlle Rousse, M. Ati, Brent C. Melot, Jean-Noël Chotard, Jean-Marie Tarascon, and Marine Reynaud

Subjects
Chemistry, Inorganic chemistry, Neutron diffraction, Structure (category theory), 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 3. Good health, 0104 chemical sciences, Inorganic Chemistry, Crystallography, Octahedron, Trans configuration, Antiferromagnetism, Magnetic phase transition, Physical and Theoretical Chemistry, 0210 nano-technology, Ground state, Néel temperature
Abstract

A novel hydrated fluoroselenate NaCoSeO(4)F·2H(2)O has been synthesized, and its structure determined. Like its sulfate homologue, NaCoSO(4)F·2H(2)O, the structure contains one-dimensional chains of corner-sharing MO(4)F(2) octahedra linked together through F atoms sitting in a trans configuration with respect to each other. The magnetic properties of the two phases have been investigated using powder neutron diffraction and susceptibility measurements which indicate antiferromagnetic ordering along the length of the chains and result in a G-type antiferromagnetic ground state. Both compounds exhibit a Néel temperature near 4 K, and undergo a field-induced magnetic phase transition in fields greater than 3 kOe.

Published
2011

36. Structural Polymorphism in Na4Zn(PO4)2Driven by Rotational Order–Disorder Transitions and the Impact of Heterovalent Substitutions on Na-Ion Conductivity

Author

Saha, Sujoy, Rousse, Gwenaëlle, Courty, Matthieu, Shakhova, Yaroslava, Kirsanova, Maria, Fauth, François, Pomjakushin, Vladimir, Abakumov, Artem M., and Tarascon, J. M.

Abstract

Solid electrolytes have regained tremendous interest recently in light of the exposed vulnerability of current rechargeable battery technologies. While designing solid electrolytes, most efforts concentrated on creating structural disorder (vacancies, interstitials, etc.) in a cationic Li/Na sublattice to increase ionic conductivity. In phosphates, the ionic conductivity can also be increased by rotational disorder in the anionic sublattice, via a paddle-wheel mechanism. Herein, we report on Na4Zn(PO4)2which is designed from Na3PO4, replacing Na+with Zn2+and introducing a vacancy for charge balance. We show that Na4Zn(PO4)2undergoes a series of structural transitions under temperature, which are associated with an increase in ionic conductivity by several orders of magnitude. Our detailed crystallographic study, combining electron, neutron, and X-ray powder diffraction, reveals that the room-temperature form, α-Na4Zn(PO4)2, contains orientationally ordered PO4groups, which undergo partial and full rotational disorder in the high-temperature β- and γ-polymorphs, respectively. We furthermore showed that the highly conducting γ-polymorph could be stabilized at room temperature by ball-milling, whereas the β-polymorph can be stabilized by partial substitution of Zn2+with Ga3+and Al3+. These findings emphasize the role of rotational disorder as an extra parameter to design new solid electrolytes.

Published
2020
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37. Structural Instability Driven by Li/Na Competition in Na(Li1/3Ir2/3)O2Cathode Material for Li-Ion and Na-Ion Batteries

Author

Perez, Arnaud J., Rousse, Gwenaëlle, and Tarascon, Jean-Marie

Abstract

With increasing hopes placed on the Na-ion battery technology to complement the current Li-ion battery systems, it is important to improve the energy density of Na-based cathode materials. Na-rich rocksalt oxides, Na1+xM1–xO2(M = transition metal), combining cationic and anionic redox activity, could provide the necessary increase in capacity to achieve this goal, but their synthesis remains challenging compared to the Li analogues. As an alternative, mixed compounds Na(AxM1–x)O2, with A being an electropositive cation such as Li, Mg, or Zn sitting in the transition-metal layer, have been reported. As a continuation, we herein prepared the mixed Na(Li1/3Ir2/3)O2phase and compared its structure and electrochemical properties with the well-known Li2IrO3and Na2IrO3parent materials. By mixing Na and Li in the material, the stacking sequence of the transition-metal honeycomb layers in Na(Li1/3Ir2/3)O2is modified compared to the two parent materials, resulting in the presence of extra superstructure peaks in X-ray diffraction data. Using electrochemical characterization and an in-situ X-ray diffraction technique, the mixed Na(Li1/3Ir2/3)O2was found to be unstable both in Li and Na batteries and to separate into Na-rich NaxIrO3and Li-rich LixIrO3phases due to the competition between electrochemical (de)insertion, cation exchange with the electrolyte, and segregation of Na and Li in the material. These findings highlight important challenges and offer useful insight into guide the design of new mixed Na(AxM1–x)O2cathode materials with high capacity for Na-ion batteries.

Published
2019
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40. Magnetic structures of LiMBO3 (M = Mn, Fe, Co) lithiated transition metal borates

Author

Tyrel M. McQueen, Gwenaëlle Rousse, Brent C. Melot, James R. Neilson, Liang Tao, and Christian Masquelier

Subjects
Condensed matter physics, Magnetic moment, Chemistry, Plane (geometry), chemistry.chemical_element, Inorganic Chemistry, Magnetization, Crystallography, Transition metal, Ferromagnetism, Moment (physics), Antiferromagnetism, Condensed Matter::Strongly Correlated Electrons, Physical and Theoretical Chemistry, Boron
Abstract

The magnetic ordering within LiMBO3 compounds (M = Mn, Fe, and Co) has been explored by magnetization measurements and neutron powder diffraction. For all M, an incommensurately ordered magnetic phase is established on cooling, followed by a change to a commensurate long-range antiferromagnetic state below TN2 = 12(1) K for LiMnBO3, TN2 = 25(1) K for LiFeBO3, and TN2 = 12(1) K for LiCoBO3. For LiMnBO3, the magnetic ordering at T = 2 K exhibits a propagation vector k = (1, 0, 0) and consists of antiferromagnetic chains that are coupled antiferromagnetically to each other, the magnetic moments being oriented along the [001] direction. In contrast, the magnetic order at T = 2 K in LiFeBO3 and LiCoBO3 exhibits a propagation vector of k = (1/2, 1/2, 1/2) and consists of ferromagnetic chains that are antiferromagnetically coupled. The magnetic moments lie roughly along the [023] direction within the bc plane for LiFeBO3, and along the [301] direction within the ac plane for LiCoBO3. The moment orientations in both LiMnBO3 and LiFeBO3 suggest an Ising character arising from unquenched orbital momentum due to unusual trigonal bipyrimidal coordination environments. No evidence of Ising behavior is found in the case of LiCoBO3.

Published
2013

41. Marinite Li2M(SO4)2 (M = Co, Fe, Mn) and Li1Fe(SO4)2: model compounds for super-super-exchange magnetic interactions

Author

Jean-Noël Chotard, Jean-Marie Tarascon, Juan Rodríguez-Carvajal, Gwenaëlle Rousse, and Marine Reynaud

Subjects
Inorganic Chemistry, Neutron powder diffraction, Battery (electricity), Transition metal, Chemistry, Magnetism, Metallurgy, Electrode, Analytical chemistry, New materials, Physical and Theoretical Chemistry, Magnetic study
Abstract

New materials initially designed for battery electrodes are often of interest for magnetic study, because their chemical compositions include 3d transition metals. We report here on the magnetic properties of marinite phases Li2M(SO4)2 (M = Fe, Co, Mn) and Li1Fe(SO4)2, which all order antiferromagnetically at low temperature. From neutron powder diffraction, we propose a model for their ground-state magnetic structures. The magnetism of marinite Li2M(SO4)2 compounds unambiguously results from super-super-exchange interactions; therefore, these materials can be considered as a model case for which the Goodenough–Kanamori–Anderson rules can be tested.

Published
2013

42. Neutron diffraction study of the Li-ion battery cathode Li2FeP2O7

Author

Atsuo Yamada, Yannick Klein, Prabeer Barpanda, Chris D. Ling, Zakiah Mohamed, Tian Ye, Gwenaëlle Rousse, Department of Chemical System Engineering, The University of Tokyo, The University of Tokyo (UTokyo), Unit of Element Strategy Initiative for Catalysts & Batteries, ESICB, Kyoto University, Kyoto University [Kyoto], Institut de minéralogie, de physique des matériaux et de cosmochimie (IMPMC), Muséum national d'Histoire naturelle (MNHN)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de recherche pour le développement [IRD] : UR206-Centre National de la Recherche Scientifique (CNRS), School of Chemistry, The University of Sydney, The University of Sydney, and Kyoto University

Subjects
Magnetic moment, Condensed matter physics, Magnetic structure, Chemistry, Inorganic chemistry, Neutron diffraction, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Magnetic susceptibility, Cathode, 0104 chemical sciences, law.invention, Inorganic Chemistry, Ferromagnetism, [PHYS.QPHY]Physics [physics]/Quantum Physics [quant-ph], law, Antiferromagnetism, Condensed Matter::Strongly Correlated Electrons, Physical and Theoretical Chemistry, 0210 nano-technology, Monoclinic crystal system
Abstract

International audience; With a combination of magnetic susceptibility measurements and lowtemperature neutron diffraction analyses, the magnetic structure of Li2FeP2O7 cathode has been solved. This pyrophosphate Li2FeP2O7 compound stabilizes into a monoclinic framework (space group P21/c), having a pseudolayered structure with the constituent Li/Fe sites distributed into MO6 and MO5 building units. The magnetic susceptibility follows a Curie−Weiss behavior above 50 K. Li2FeP2O7 shows a long-range antiferromagnetic ordering at TN = 9 K, as characterized by the appearance of distinct additional peaks in the neutron diffraction pattern below TN. Its magnetic reflections can be indexed with a propagation vector k = (0,0,0). The magnetic moments inside the FeO6−FeO5 clusters are ferromagnetic, whereas these clusters are antiferromagnetic along the chains. The adjacent chains are in turn ferromagnetically arranged along the a-axis. The magnetic structure of Li2FeP2O7 cathode material is described focusing on their localized spin−spin exchange. The magnetic structure and properties have been generalized for Li2FeP2O7−Li2CoP2O7 binary solid solutions

Published
2013

45. Influence of Temperature-Driven Polymorphism and Disorder on Ionic Conductivity in Li6Zn(P2O7)2

Author

Saha, Sujoy, Rousse, Gwenaëlle, Fauth, François, Pomjakushin, Vladimir, and Tarascon, Jean-Marie

Abstract

Ionic conductivity in a compound is rooted in a delicate interplay between its crystal structure and its structural defects (vacancies, interstitials, etc.). Hence, understanding this interplay is of utmost importance to design new solid state electrolytes. To shed some light on the above query, we investigated the rich crystal chemistry of Li6Zn(P2O7)2. This compound undergoes multiple structural transitions under the influence of temperature, which increases the conductivity by several orders and lowers the activation energy. We explained this jump in conductivity by the increased disorder associated with cation mixing. Our structural exploration indicates that both the room-temperature α-polymorph and the high-temperature ζ-polymorph crystallize in a C2/cspace group but with a much smaller unit cell volume for the latter. While their structural framework based on P2O74–is similar, the ζ-polymorph presents a fully disordered Li/Zn sublattice, while it is fully ordered for the α-polymorph. Furthermore, the bond valence energy landscape calculations show that in the α-polymorph, the Li+conduction is two-dimensional, whereas because of Li+/Zn2+site mixing, Li+can hop three-dimensionally in the ζ-polymorph.

Published
2019
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